DE2218328C3 - Propellant mixture - Google Patents

Description

R ₄ X

can represent, where π can vary from 0 to 4, the radicals K ₁ , Rj and R _{4 have} the meaning already given and X is hydrogen or straight-chain or branched alkyl radicals with 1 to 4 carbon atoms, according to 'atent 2! 26 146 in combination with compounds that split off or contain acidic or basic constituents as propellants for the production of cellular or porous plastic articles.

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The subject of patent 21 26 146 is the use of benzoxazines of the general formula I.

R ₁ O

4Ί

R,

III

i i

R ₄ X

in which R 1 to R _{4 are} hydrogen, straight-chain or branched alkyl radicals having 1 to 4 carbon atoms, hydroxyl or nitro groups or halogen atoms, and Rj is also a molecular radical of the following formula

R ₁ O

K ₄ X

can represent, where η can vary from 0 to 4, the radicals Ri, R ₃ and Rt have the meaning already given and X is hydrogen or straight-chain or branched alkyl radicals with 1 to 4 carbon atoms, as a blowing agent for the production of cellular or porous plastic articles.

In addition, it has now been found that these propellants are used in combination with compounds that split off or contain acidic or basic components.

The invention thus relates to the use of benzoxazines of the general formula 1

in which R 1 to R _{4 are} hydrogen, straight-chain or branched alkyl radicals with 1 to 4 hydrogen atoms, hydroxyl or nitro groups or halogen atoms, and R 2 is also a molecular radical of the following formula

R,

R, O

la R ₄ X

in which Rj to R ₄ denote hydrogen, straight-chain or branched alkyl radicals with 1 to 4 carbon atoms, hydroxyl or nitro groups or halogen atoms, and R2 also denotes a molecular radical of the following formula

I.),,

R, O

Γ ϊ ι

R, I I ο

R ₄ X

can represent ftr, where η can vary from 0 to 4, the radicals Ri, Rj and R _{4 have} the meaning already listed and X is hydrogen or straight-chain or branched alkyl radicals with 1 to 4 carbon atoms, according to main palent 21 26 146 in combination with acid or compounds which split off or contain basic constituents as propellants for the production of oval or porous plastic articles.

By adding the auxiliary ink according to the invention the decomposition temperature of the compounds of general formula I is reduced. Farther the foam structure of the extruded plastics is surprisingly fine-pored and the gas yield is increased more than proportional to the amount of auxiliary propellant added.

Examples of suitable compounds of the general formula I are:

N-methyl isatoic anhydride.

5-Hydroxyisatosäureanhydnd.

5-Chlorisatosaurcanhydnd.

J.5-dichloro acid anhydride,

5-Broffiisato anhydride,

3,5-dibromisalosic anhydride,

iv nitrous acid anhydride,

Isatoic anhydride,

N ^ ethyl ^ dhlof isatoic anhydride,

N'Methyl-S-nilroisalosatircanhydnd,

5-methylisaloic acid afihydride,

5-ethylisali acid anhydride,

5'n'Propylisatosätircanhydrid,

5-Isopropylis toic anhydride, S-terL-butylisatoic anhydride, 4-methylisatoic anhydride, 4-ethylisatoic anhydride,

4-n-propylene acid anhydride, %

4-isopropylisatoic anhydride, 4-n-Butylisatoic anhydride, 4-IsobuiyIisatoic anhydride, 4-terL-butylisatoic anhydride,

Bisisatoic anhydride and m

Methylene-bis-isatoic anhydride.

Preferably used;

Isatoic anhydride, r>

5-chloroisatoic anhydride and 5-nitroisatoic anhydride.

The compounds are used in amounts of 0.01 -jō, preferably 1 - 0 weight percent, based on the i "plastic, added.

As typical representatives of the auxiliaries are Ammonium carbonate, ammonium chloride, urea, dicyandiamide, disulfohydrazide, azodicarbonamide, N-methyl diethanolamine and triethanolamine listed, r, Azodicarbonamide and disulfohydrazides are preferred.

Compounds with the following structure are regarded as disulfohydrazides:

H ₂ N-NHSO ₂ -R-SO ₂ NH-NH ^,! "

where R is an aromatic radical such as. B. phenyl, naphthyl. Means antracenyl, diphenylene, etc. in the In the case of non-fused aromatics, such as B. Diphenylene, the bond between the aromatics can r> be interrupted by heteroatoms, e.g. B. in diphenylene oxide or diphenylene sulfone.

These compounds are used in amounts of 0.01 to 1% by weight. b preferably 0.1 to 0.5% by weight. Based on the Plastic slipper. admitted. 4n

The drawing shows the more than proportional increase in the gas yield in the individual curves with one another at different amounts of propellant added, curve I being a mixture of Isatosäure.inhydrid and A / odicarbonamid according to Bei- 4 ". game I. Curve 2 is a mixture of isatoic anhydride and diphenylene oxide disulfohydrazide according to Example 2 and Curve 3 represents isatoic anhydride according to Example 3.

The propellant mix is for the production of thermoplastic plastics suitable, for example vi these are:

Polystyrene. Polyethylstyrene, Polyulkylcn.

Polyvinyl chloride. Polyvinyl acetate,

Polymethacrylate. Polymethacrylonitrile. -, -,

Pulyjcrylnitril, polyamide. Polyurethane, Polycarbonate, polysulfones.

Polyethylene terephthalate. Polyacetals.

Polyphenylene oxides.

thermoplastics based on «> Cellulose esters and copolymers from the listed components.

Furthermore, mixtures of various thermoplastic polymers and so-called thcr- _a <·, möplastischeri Mehfph r: en-plastics are used for the production of foams, such as:

Acrylonitrile-styrene-butadiene polymers, mixtures of polysulfone and styrene-acrylonitrile or Acrylonitrile butadiene styrene polymers,

Mixtures of polyphenylene oxide and polystyrene, Mixtures of polyacetal and polyurethane, mixtures of polycarbonate and acrylonitrile-butadiene-styrene polymers, Mixtures of polyvinyl chloride with acrylonitrile-butadiene-styrofoam polymers or with ethylene-vinyl acetate copolymers, mixtures of polystyrene with rubber-elastic ones Mixed or segmented polymers based on butadiene, styrene, styrene-acrylonitrile copolymers with butadiene-acrylonitrile polymers.

In a preferred embodiment Use two-phase plastics, i where the haritr phase based on Poiyst; roi or one Copolymer of styrene and alkyl or halostyrene is modified with a kauischukelastic phase on the basis of butadiene impact-resistant.

Ks v. Are preferably used two-phase plastics, in which the hard phase is based on copolymers of styrene and / or alkylstyrene and / or Methyl methacrylate with acrylonitrile with a rubber elastic Phase based on butadiene and / or acrylic acid esters with 1 -6 in aliphatic or cycloaliphatic Chain located carbon atoms in the alcohol component is modified impact-resistant. as Rubber-elastic phase can also be other diene rubbers based on isoprene or cyclopentadiene can be used as well as copolymers of butadiene and styrene. Butadiene and acrylonitrile, or Ethylene-vinyl acetate copolymers or ethylene-propylene terpolymers. for example with Die.ien βλ Terkomponcnte.

Two-phase plastics are very particularly preferred. where the hard phase is based on styrene and / or alkylstyrene and acrylonitrile with a rubber-elastic phase based on butadiene Is modified impact-resistant, for example in a Composition of 5-60 percent by weight of butadiene polymer with not more than 30% copolymerized tem styrene. Isoprene or acrylonitrile, and 95-40 percent by weight polymerized styrene and acrylonitrile in a weight ratio of 90:10 to 50:50 Styrene in whole or in part by nc-methylstyrene or Methacrylic acid methyl ester can be replaced.

The propellant mixture used according to the invention can be mixed into the mixtures to be foamed in a conventional manner, for example on Mixing rollers in internal mixers or in stirrers equipped mixing tanks; the individual components can also be / ugeset / t simultaneously with the addition of other mixture components.

The mixtures can also be other known ones Contain auxiliary materials. /. B. active or inactive fillers [gf Fe, such as soot or chalk, antioxidants, ank? zonants, Stabilizers such as B. salts of bid, cadmium, calcium, zinc, tin, barium, and waxes, Dyes, pigments, zinc oxide, fatty acids, e.g. B. stearic acid, mineral oils, plasticizers such. B. dioctyl phthalate, Butyl nonyl phthalate, butyl benzyl phthalate, dibutyl phthalal, Dibutyl adipate, tricresylphosphate, lubricants or peroxides,

The manufacture Her Vefhinrliinupn r \ pr ηΙΙσπΓηριηρπ

Formula I is carried out in a known manner, for. B. according to Organic Synthesis GoII Vol. IH ₁ p.488, by reacting the corresponding anthranil drinks or in an analogous manner by converting benzidine-3,3'-dicarboxylic acid or 4,4'-diaminodiphenylmethyl-3,3'- dicarboxylic acid with phosgene.

The use according to the invention is through the The following examples are described without being restricted thereto.

example 1

A mixture of 3000 parts by weight of a Pfropfpolyrnerisales of 17.5% butadiene, 59.5% styrene and 23% acrylonitrile, 90 GewichtsteÜen Bulylstearät, 90 Gewichlsteilen isatoic anhydride and 3 Gewichtsteiien azodicarbonamide was ühd via a twin screw extruder at temperatures between 12O ⁰ G

10 (45 ° C granulated. The granules on a Spritzgüßmaschine at a specific spray ^ was pressure of 800 kp / cm ² and processed a melt temperature of 24O ⁰ G to give moldings. There is obtained a fine-pored! Foam with regular foam structure and a density of 0.60 g / cm ³ .

Example 2

Analogously to Example 1, 3 parts by weight of diphenylene oxide disulfohydrazide are used as blowing agent additive. A foam with a regular pore structure and a bulk density of 0.62 g / cm ^{3 is obtained} .

Example 3

Analogously to Example I, 90 parts by weight of isatoic anhydride are used. A foam with a coarse foam structure and a density of 0.64 g / cm ^{3 is obtained} .

1 sheet of drawings

Claims (1)

Claim: Use of benzoxazines of the general formula 1 (I) IO (CH ₂ ),